涡阳花沟西10煤中微量元素的赋存状态及环境效应
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摘要
为探明涡阳花沟西10煤中微量元素的赋存状态和环境效应,给10煤煤炭资源的开采和合理利用提供科学依据,共收集10个钻孔煤样品,分别对该研究区10煤中微量元素的富集情况、赋存状态和挥发性进行了研究,并以研究区10煤层为例,探讨了基于模糊综合评判的三级(洁净煤、一般煤和不洁净煤)煤洁净程度评价方法。
采用电感耦合等离子质谱仪(ICP-MS)分析了煤中13种微量元素的含量,与华北煤、中国煤和世界煤相应元素的丰度值相比,大多数元素的含量属于“正常”或“低”质量分数水平；从相对于地壳、中国大陆岩石和土壤的富集系数可以看出：大多数样品中元素轻微富集或不富集。
应用LECO碳硫分析仪测定了煤的总有机碳(TOC),其与微量元素含量的相关关系分析表明：Be、Ba、Zn和Mo兼有有机亲和性和无机亲和性,但Be和Ba以无机亲和性为主,Zn和Mo两者相当；V、Cr、Co、Ni、Cu、Sb、Pb和T1主要具有无机亲和性；Cd主要具有有机亲和性。
X射线衍射(XRD)分析结果表明：10煤中的无机组分主要含有粘土矿物高岭石,碳酸盐矿物铁白云石、菱铁矿和方解石等,部分含有石英、黄铁矿、白云母和方铁锰矿
聚类分析表明：10煤中13种微量元素可分为两大类,其中V、Sb、Cu、Cr、Pb、Co、Ni、Tl、Mo、Be和Ba等11种元素,为铝硅酸盐吸附类,部分可能与碳酸盐矿物结合；Zn和Cd两种元素,为有机结合类,Cd以有机结合态为主。
因子分析表明：前三个因子的累积贡献率为86.39%,因子F1中V、Cr、Co、Ni、Cu、Sb、Pb和Ba有较高因子载荷,因子F2中Be、T1和Mo有较高因子载荷,因子F3中Zn和Cd有较高的因子载荷,因子F1为无机结合态因子(铝硅酸盐因子),因子F2为赋存状态不确定因子,F3为有机结合态因子。
1100℃静态燃烧实验表明：Be、Cr、Co、Ni、Cu、Zn、Sb和Ba为中等挥发,Mo和V的挥发性不确定,Pb、Tl和Cd易挥发,10煤中Pb和T1含量相对较高,在煤炭资源的利用过程中需注意其危害。
以部分原煤煤质参数,有害微量元素的含量、挥发性和赋存状态,煤的工艺特征为评价指标,根据微量元素的毒性确定元素权重,并采用模糊综合评判的方法,对研究区10煤层煤的洁净程度进行了分析评价。评价结果表明：涡阳花沟西10煤属洁净煤。
In order to investigate the modes of occurrence and environmental effects of trace elements in coal from No.10 coal-bed at western Huagou, and to provide scientific basis for rational exploitation and utilization of the coal resources in this area,10 coal samples were collected from the cores of different boreholes, the enrichment, modes of occurrence, and volatility of trace elements were measured by various methods. Finally, a three-graded clean degree assessment method of coal based on fussy comprehensive evaluation were discussed and applied in assessing the cleanliness of coal resources from No.10 coal-bed.
The concentrations of 13 kind trace elements were determined using inductively coupled plasma mass spectrometry (ICP-MS). Most trace elements are of normal or low levels compared with its Clarkes in Northern China, Chinese and world coals. Trace elements are slightly enriched or non-enriched in major coal sample, which could be concluded from the enrichment factor related to their contents in the crust, and rock and soil of Chinese continent.
Total organic carbon (TOC) of the coal was measured by LECO carbon and sulfur analyzer. The correlations between TOCs and concentrations of trace elements indicate that Beryllium, Ba, Zn, and Mo are associated with organic matter and minerals in coal, but Beryllium and Ba are mainly in minerals, however, Zinc and Mo are evenly distributed in organic and inorganic matter. Vanadium, Cr, Co, Ni, Cu, Sb, Pb and Tl have strongly inorganic affinity, while cadmium is on the contrary.
Inorganic matters of No.10 coal are mainly consist of clay minerals such as kaolinite, and carbonate mineral siderite and calcite. Quartz, pyrite, muscovite and bixbyite are detected in individual coal samples by X-ray diffraction (XRD).
Cluster analysis result demonstrates that eleven trace elements belong to adsorption species by alumino-silicate, or partially locate in carbonate minerals, Vanadium, Sb, Cu, Cr, Pb, Co, Ni, Tl, Mo, Be and Ba included. Zinc and Cd pertain to organic combination, and the latter mainly associated with organics.
Factor analysis illustrates that all thirteen trace elements can be expressed by three factors, F1, F2 and F3, respectively. Vanadium, Cr, Co, Ni, Cu, Sb, Pb and Ba have large factor loading in F1. Beryllium, Tl and Mo are significant in F2. Zinc and Cd are important in F3. too. According to the modes of occurrence of trace elements, F1 can be designated as inorganic association factor or aluminosilicate factor, F3 may be named organic combination factor, nevertheless F2 is uncertain factor because the occurrence of the three trace elements aren't definitive as others.
Trace elements in coal could be classified into three groups based on their volatilities in combustion process. Beryllium, Cr, Co, Ni, Cu, Zn, Sb and Ba moderately volatilize in combustion and uniformly distribute in bottom and fly ash. While Lead, Tl and Cd easily form vapor and escape the stack or pollution control devices as gaseous phase or aerosol. Thus, precaution and protective measures should be taken when utilize the coal from No.10 coal-bed at western Huagou owing to easy volatility and relatively high contents of Lead, Tl and Cd. The volatilities of Molybdenum and V are uncertain because experimental error.
Choosing some parameters of raw coal including ash yields, sulfur contents, the contents, volatility and modes of occurrence of trace elements, and technical characteristics as evaluating index, and assigning the weight of the third evaluating indice according to the toxicity of trace elements, and then build a completed clean degree evaluation system for coal using fuzzy comprehensive evaluation method. At last, the evaluation system is applied in the assessment of cleanliness of coal from No.10 coal-bed at western Huagou, and the results show that the coal resources of No.10 coal-bed is clean and have little environmental effects and healthy implications.
采用电感耦合等离子质谱仪(ICP-MS)分析了煤中13种微量元素的含量,与华北煤、中国煤和世界煤相应元素的丰度值相比,大多数元素的含量属于“正常”或“低”质量分数水平；从相对于地壳、中国大陆岩石和土壤的富集系数可以看出：大多数样品中元素轻微富集或不富集。
应用LECO碳硫分析仪测定了煤的总有机碳(TOC),其与微量元素含量的相关关系分析表明：Be、Ba、Zn和Mo兼有有机亲和性和无机亲和性,但Be和Ba以无机亲和性为主,Zn和Mo两者相当；V、Cr、Co、Ni、Cu、Sb、Pb和T1主要具有无机亲和性；Cd主要具有有机亲和性。
X射线衍射(XRD)分析结果表明：10煤中的无机组分主要含有粘土矿物高岭石,碳酸盐矿物铁白云石、菱铁矿和方解石等,部分含有石英、黄铁矿、白云母和方铁锰矿
聚类分析表明：10煤中13种微量元素可分为两大类,其中V、Sb、Cu、Cr、Pb、Co、Ni、Tl、Mo、Be和Ba等11种元素,为铝硅酸盐吸附类,部分可能与碳酸盐矿物结合；Zn和Cd两种元素,为有机结合类,Cd以有机结合态为主。
因子分析表明：前三个因子的累积贡献率为86.39%,因子F1中V、Cr、Co、Ni、Cu、Sb、Pb和Ba有较高因子载荷,因子F2中Be、T1和Mo有较高因子载荷,因子F3中Zn和Cd有较高的因子载荷,因子F1为无机结合态因子(铝硅酸盐因子),因子F2为赋存状态不确定因子,F3为有机结合态因子。
1100℃静态燃烧实验表明：Be、Cr、Co、Ni、Cu、Zn、Sb和Ba为中等挥发,Mo和V的挥发性不确定,Pb、Tl和Cd易挥发,10煤中Pb和T1含量相对较高,在煤炭资源的利用过程中需注意其危害。
以部分原煤煤质参数,有害微量元素的含量、挥发性和赋存状态,煤的工艺特征为评价指标,根据微量元素的毒性确定元素权重,并采用模糊综合评判的方法,对研究区10煤层煤的洁净程度进行了分析评价。评价结果表明：涡阳花沟西10煤属洁净煤。
In order to investigate the modes of occurrence and environmental effects of trace elements in coal from No.10 coal-bed at western Huagou, and to provide scientific basis for rational exploitation and utilization of the coal resources in this area,10 coal samples were collected from the cores of different boreholes, the enrichment, modes of occurrence, and volatility of trace elements were measured by various methods. Finally, a three-graded clean degree assessment method of coal based on fussy comprehensive evaluation were discussed and applied in assessing the cleanliness of coal resources from No.10 coal-bed.
The concentrations of 13 kind trace elements were determined using inductively coupled plasma mass spectrometry (ICP-MS). Most trace elements are of normal or low levels compared with its Clarkes in Northern China, Chinese and world coals. Trace elements are slightly enriched or non-enriched in major coal sample, which could be concluded from the enrichment factor related to their contents in the crust, and rock and soil of Chinese continent.
Total organic carbon (TOC) of the coal was measured by LECO carbon and sulfur analyzer. The correlations between TOCs and concentrations of trace elements indicate that Beryllium, Ba, Zn, and Mo are associated with organic matter and minerals in coal, but Beryllium and Ba are mainly in minerals, however, Zinc and Mo are evenly distributed in organic and inorganic matter. Vanadium, Cr, Co, Ni, Cu, Sb, Pb and Tl have strongly inorganic affinity, while cadmium is on the contrary.
Inorganic matters of No.10 coal are mainly consist of clay minerals such as kaolinite, and carbonate mineral siderite and calcite. Quartz, pyrite, muscovite and bixbyite are detected in individual coal samples by X-ray diffraction (XRD).
Cluster analysis result demonstrates that eleven trace elements belong to adsorption species by alumino-silicate, or partially locate in carbonate minerals, Vanadium, Sb, Cu, Cr, Pb, Co, Ni, Tl, Mo, Be and Ba included. Zinc and Cd pertain to organic combination, and the latter mainly associated with organics.
Factor analysis illustrates that all thirteen trace elements can be expressed by three factors, F1, F2 and F3, respectively. Vanadium, Cr, Co, Ni, Cu, Sb, Pb and Ba have large factor loading in F1. Beryllium, Tl and Mo are significant in F2. Zinc and Cd are important in F3. too. According to the modes of occurrence of trace elements, F1 can be designated as inorganic association factor or aluminosilicate factor, F3 may be named organic combination factor, nevertheless F2 is uncertain factor because the occurrence of the three trace elements aren't definitive as others.
Trace elements in coal could be classified into three groups based on their volatilities in combustion process. Beryllium, Cr, Co, Ni, Cu, Zn, Sb and Ba moderately volatilize in combustion and uniformly distribute in bottom and fly ash. While Lead, Tl and Cd easily form vapor and escape the stack or pollution control devices as gaseous phase or aerosol. Thus, precaution and protective measures should be taken when utilize the coal from No.10 coal-bed at western Huagou owing to easy volatility and relatively high contents of Lead, Tl and Cd. The volatilities of Molybdenum and V are uncertain because experimental error.
Choosing some parameters of raw coal including ash yields, sulfur contents, the contents, volatility and modes of occurrence of trace elements, and technical characteristics as evaluating index, and assigning the weight of the third evaluating indice according to the toxicity of trace elements, and then build a completed clean degree evaluation system for coal using fuzzy comprehensive evaluation method. At last, the evaluation system is applied in the assessment of cleanliness of coal from No.10 coal-bed at western Huagou, and the results show that the coal resources of No.10 coal-bed is clean and have little environmental effects and healthy implications.
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